WO2002006196A1 - Composes chiraux i - Google Patents

Composes chiraux i Download PDF

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Publication number
WO2002006196A1
WO2002006196A1 PCT/EP2001/007217 EP0107217W WO0206196A1 WO 2002006196 A1 WO2002006196 A1 WO 2002006196A1 EP 0107217 W EP0107217 W EP 0107217W WO 0206196 A1 WO0206196 A1 WO 0206196A1
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Prior art keywords
chiral
group
compounds
liquid crystalline
formula
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PCT/EP2001/007217
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English (en)
Inventor
Peer Kirsch
Andreas Taugerbeck
Detlef Pauluth
Joachim Krause
Kazuaki Tarumi
Michael Heckmeier
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Merck Patent Gmbh
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Priority to AU2001266092A priority Critical patent/AU2001266092A1/en
Priority to JP2002512103A priority patent/JP5265838B2/ja
Priority to EP01943543A priority patent/EP1299334B1/fr
Priority to KR1020037000358A priority patent/KR100849981B1/ko
Priority to US10/332,470 priority patent/US7060331B2/en
Priority to DE60132456T priority patent/DE60132456T2/de
Publication of WO2002006196A1 publication Critical patent/WO2002006196A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/58—Dopants or charge transfer agents
    • C09K19/586—Optically active dopants; chiral dopants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition

Definitions

  • the invention relates to chiral compounds, to liquid crystalline mixtures containing one or more of these chiral compounds, to polymers obtained from these liquid crystalline mixtures, and to the use of these chiral compounds, liquid crystalline mixtures and polymers obtained thereof in liquid crystal displays, active and passive optical elements like polarizers, compensators, alignment layers, colour filters or holographic elements, in adhesives, synthetic resins with anisotropic mechanical properties, cosmetic and pharmaceutical compositions, diagnostics, liquid crystal pigments, for decorative, and security applications, in nonlinear optics, optical information storage or as chiral dopants.
  • Chiral compounds can be used as dopants to induce or enhance a helical twist in a liquid crystalline mixture that is used for example in liquid crystal displays.
  • the pitch p of the molecular helix in the first approximation which is sufficient for most practical applications, is inversely proportional to the concentration c of the chiral dopant in the liquid crystal host mixture according to equation (1) :
  • the proportionality factor is the helical twisting power (HTP) of the chiral dopant.
  • phase-change displays guest- host displays, passive and active matrix TN and STN displays like AMD-TN, ferroelectric displays and cholesteric displays like SSCT (surface stabilized cholesteric texture) or PSCT (polymer stabilized cholesteric texture) displays, including displays with temperature compensated characteristics, e.g. by appropriate selection of the cholesteric compounds according to the invention either alone or in combination with further chiral dopants.
  • SSCT surface stabilized cholesteric texture
  • PSCT polymer stabilized cholesteric texture
  • LC mixtures that exhibit a strong helical twist and thereby a short pitch length.
  • the pitch has to be selected such that the maximum of the wavelength reflected by the cholesteric helix is in the range of visible light.
  • polymer films with a chiral liquid crystalline phase for optical elements such as cholesteric broadband polarizers or chiral liquid crystalline retardation films.
  • a short pitch can be achieved by using high amounts of dopant or by using a dopant with a high HTP.
  • Chiral compounds are disclosed for example in WO 95/16007 and WO 98/00428.
  • the chiral dopants of prior art often exhibit low values of the HTP, so that high amounts of dopant are needed. This is a disadvantage because chiral dopants can be used only as pure enantiomers and are therefore expensive and difficult to synthesize.
  • the invention has the aim of providing chiral compounds having these properties, but which do not have the disadvantages of the chiral dopants of the state of the art as discussed above.
  • Another aim of the invention is to extend the pool of chiral compounds that can be used as dopants available to the expert.
  • R 1 and R 2 are independently of each other F, Cl, Br, ON, SON, SF 5) a chiral or achiral alkyl group with up to 30 C atoms which may be unsubstituted, mono- or polysubstituted by F, Cl, Br or ON, it being also possible for one or more non-adjacent CH 2 groups to be replaced, in each case independently from one another, by - 0-, -S-, -NH-, -N(CH 3 )-, -CO-, -COO-, -OCO-, -OCO-0-, -S-CO-,
  • R 3 is H or alkyl with 1 to 4 C atoms
  • a 1 and A 2 are independently from one another 1 ,4-phenylene in which, in addition, one or more CH groups may be replaced by N, 1 ,4-cyclohexylene in which, in addition, one or two non- adjacent CH 2 groups may be replaced by O and/or S, 1,3- dioxolane-4,5-diyl, 1 ,4-cyclohexenylene, 1 ,4-bicyclo ⁇ (2,2,2)- octylene, piperidine-1 ,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1 ,2,3,4-tetrahydronaphthaiene- 2,6-diyl, or indane-2,5-diyl,it being possible for all these groups to be unsubstituted, mono- or polysubstituted with halogen, cyano or nitro groups or alkyl, alkoxy, alky
  • n 1 , 2, 3, 4 or 5
  • inventive chiral compounds bear several advantages • they exhibit a good solubility in liquid crystalline mixtures, • they are mesogenic or even liquid crystalline, • by varying the chiral group R 1 and/or R 2 compounds with a high twisting power HTP can be obtained,
  • both the R and S enantiomers can be prepared, which allows the formation of a cholesteric phase with either a right or left handed cholesteric helix,
  • Another object of the invention is a liquid crystalline mixture containing at least one compound of formula I.
  • Another object of the present invention is a polymerizable liquid crystalline mixture comprising at least one compound of formula I and at least one polymerizable mesogenic compound having at least one polymerizable functional group.
  • Another object of the invention is a chiral linear or crosslinked liquid crystalline polymer obtainable by polymerizing a polymerizable liquid crystalline mixture comprising one or more compounds of formula I.
  • a further object of the invention is the use of a chiral compound, mixture or polymer as described above in liquid crystal displays, such as STN, TN, AMD-TN, temperature compensation, ferroelectric, guest-host, phase change or surface stabilized or polymer stabilized cholesteric texture (SSCT, PSCT) displays, in active and passive optical elements like polarizers, compensators, alignment layers, colour filters or holographic elements, in adhesives, synthetic resins with anisotropic mechanical properties, cosmetic and pharmaceutical compositions, diagnostics, liquid crystal pigments, for decorative and security applications, in nonlinear optics, optical information storage or as chiral dopants.
  • Yet another object of the invention is a liquid crystal display comprising a liquid crystalline mixture or a polymerizable liquid crystalline mixture comprising at least one chiral compound of formula I.
  • inventive chiral compounds are mesogenic or even liquid crystalline, i.e. they can induce or enhance mesophase behaviour for example in admixture with other compounds, or even exhibit one or more mesophases themselves. It is also possible that the inventive compounds show mesophase behaviour only in mixtures with other compounds, or, in case of polymerizable compounds, when being (co)polymerized. Mesogenic inventive chiral compounds are especially preferred.
  • at least one of X 1 and X 2 is - CF 2 0- or -OCF 2 -.
  • Particularly preferred compounds are those wherein m is 1 or 2 and
  • a 2 is selected of 1 ,4-phenylene and trans-1 ,4-cyclohexylene, these rings being unsubstituted or substituted in 1 to 4 positions with F, Cl, CN or alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl with 1 to 4 C- atoms. From these preferred compounds, especially preferred are those comprising a biphenyl or cyclohexylphenyl group.
  • a smaller group of preferred mesogenic groups -A 1 -(Z-A 2 ) m - is listed below.
  • Phe in these groups is 1 ,4- phenylene which may also substituted by at least one group L, with L being F, Cl, CN or an optionally fluorinated alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl group with 1 to 4 C atoms, and Cyc is 1 ,4-cyclohexylene.
  • the list of preferred mesogenic groups is comprising the following formulae as well as their mirror images
  • subformulae II-3, II-8 and II-9 wherein one or both Z between two cyclohexylene rings are -CF 2 CF 2 -, and subformulae 11-1 , II-2, II-4, II-5, II-6, II-7, and II-8, wherein one or both Z between two phenylene rings or between a phenylene and a cyclohexylene ring are -OCF 2 -, with the O atom being adjacent to the phenylene ring.
  • the other groups Z are preferably -COO-, -OCO-, -CH 2 CH 2 - or a single bond.
  • Bi ⁇ and tricyclic mesogenic groups are preferred. Further preferred are compounds wherein the mesogenic group -A 1 -(Z-A 2 ) m - comprises at least one group Phe that is substituted with one or two groups L, preferably in 3- and/or 5-position, and L is F, Cl, CH 3 , OCH 3 , CF 3 , CHF 2 , CH 2 F, OCF 3 OCHF 2 , OCH 2 F or CN.
  • L is preferably F, Cl, CN, N0 2l CH 3 , C 2 H 5 , OCH 3 , OC 2 H 5 , COCH 3 ,
  • R 1 and R 2 in formula I is an alkyl or alkoxy radical, i.e. where the terminal CH 2 group is replaced by -0-, this may be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy, furthermore methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy, for example.
  • Halogen is preferably F or Cl.
  • R 1 and R 2 in formula I can be a polar or an unpolar group.
  • a polar group they are selected from CN, N0 2 , halogen, OCH 3 , OCN, SCN, COR 5 , COOR 5 or a mono- oligo- or polyfluorinated alkyl or alkoxy group with 1 to 4 C atoms.
  • R 5 is optionally fluorinated alkyl with 1 to 4, preferably 1 to 3 C atoms.
  • R 1 and R 2 are selected of F, Cl, CN, N0 2 , OCH 3 , COCH 3 , COC 2 H 5 , COOCH 3 , COOC 2 H 5 , CF 3 , CHF 2 , CH 2 F, OCF 3 , OCHF 2 , OCH 2 F, C 2 F 5 and OC 2 F 5 , in particular F, Cl, CN, CF 3 , and OCF 3 .
  • R 1 and R 2 are preferably alkyl with up to 15 C atoms or alkoxy with 2 to 15 C atoms.
  • R 1 and R 2 in formula I can be an achiral or a chiral group. In case of a chiral group they are preferably selected according to formula III:
  • Q 1 is an alkylene or alkylene-oxy group with 1 to 9 C atoms or a single bond
  • Q 2 is an alkyl or alkoxy group with 1 to 10 C atoms which may be unsubstituted, mono- or polysubstituted by F, Cl, Br or CN, it being also possible for one or more non-adjacent CH 2 groups to be replaced, in each case independently from one another, by -C ⁇ C-, -0-, -S-, -NH-, -N(CH 3 )-, -CO-, -COO-, -OCO-, -OCO-0-, -S-CO- or -COS- in such a manner that oxygen atoms are not linked directly to one another,
  • Q 3 is F, Cl, Br, CN or an alkyl or alkoxy group as defined for Q 2 but being different from Q 2 .
  • the O atom is preferably adjacent to the chiral C atom.
  • Preferred chiral groups of formula III are 2-alkyl, 2-alkoxy, 2- methylalkyl, 2-methylalkoxy, 2-fluoroalkyl, 2-fIuoroalkoxy, 2-(2-ethin)- alkyl, 2-(2-ethin)-alkoxy, 1 ,1 ,1 -trifiuoro-2-ai y! and 1 ,1 ,1-trifluoro-2- alkoxy.
  • achiral branched group R 1 or R 2 may occasionally be of importance, for example, due to a reduction in the tendency towards crystallization.
  • Branched groups of this type generally do not contain more than one chain branch.
  • R or R 2 denote a chiral group comprising one or more aromatic or cycloaliphatic groups, which may also contain fused rings or spirocyclic groups and may also contain one or more hetero atoms, in particular N and/or O atoms.
  • Preferred chiral groups of this type are for example cholesteryl, terpenoid radicals as disclosed e.g. in WO 96/17901 , preferably selected from menthyl, neomenthyl, campheyl, pineyl, terpineyl, isolongifolyl, fenchyl, carreyl, myrthenyl, nopyl, geraniyl, linaloyl, neryl, citronellyl and dihydrocitronellyl, particularly preferably menthyl, groups selected from menthone derivatives like
  • terminal chiral sugar derivatives comprising a mono- or dicyclic radical with pyranose or furanose rings like, for example, a terminal group derived from the chiral sugars disclosed in WO 95/16007.
  • R 1 or R 2 in formula I denotes a polymerizable group P-Sp-, with
  • CH 2 CH-Phenyl-(0) k -, W being H, CH 3 or Cl and k being 0 or 1 , and
  • Sp being a spacer group having 1 to 25 C atoms or a single bond.
  • P is preferably a vinyl group, an acrylate group, a methacrylate group, a propenyl ether group or an epoxy group, especially preferably an acrylate or a methacrylate group.
  • the spacer group Sp all groups can be used that are known for this purpose to the skilled in the art.
  • Typical spacer groups are for example -(CH 2 ) P -, -(CH 2 CH 2 0) r -CH 2 CH 2 - -CH 2 CH 2 -S-CH 2 CH 2 - or -CH 2 CH 2 -NH-CH 2 CH 2 -,with p being an integer from 2 to 12 and r being an integer from 1 to 3.
  • Preferred spacer groups are ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylene-thioethylene, ethylene-N-methyl- iminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene for example.
  • Sp is denoting an alkyl or alkoxy group with 2 to 6 C atoms.
  • Straight-chain alkyl or alkoxy groups are especially preferred.
  • Q 1 is an alkylene or alkylene-oxy group with 1 to 10 C atoms or a single bond
  • Q 2 is an alkylene or alkylene-oxy group with 1 to 10 C atoms or a single bond, being different from Q 1 , and
  • Q 3 is halogen, a cyano group or an alkyl or alkoxy group with 1 to 4 C atoms different from QA
  • the O atom is preferably adjacent to the chiral C atom.
  • R has one of the meanings of R 1 in formula I or of the preferred meanings of R 1 described above,
  • R* is a chiral group having one of the meanings of R 1 in formula I or of the preferred meanings of R 1 described above,
  • X is OCF 2 or CF 2 0, preferably CF 2 0,
  • Y is F, Cl, CN, CF 3 , CHF 2 , CH 2 F, OCF 3 , OCHF 2 , OCH 2 F, C 2 F 5 or OC 2 F 5 ,
  • Z is -COO-, -OCO-, -CH 2 CH 2 -, -CF 2 CF 2 -, -CF 2 0- or -OCF 2 -, and
  • L ⁇ L 2 , L 3 , L 4 , L 5 and L 6 are independently of each other H or F.
  • R in these preferred compounds is preferably an achiral group.
  • R* in these preferred compounds is very preferably
  • o is 0 or 1 , with o being 0 in case R* is adjacent to a CF 2 0 group, and n is an integer from 2 to 12, preferably from 3 to 8, very preferably 4, 5 or 6.
  • the asterisk * indicates a chiral C atom.
  • inventive chiral compounds can be synthesized according to or in analogy to the methods described in A. Haas et al., Chem. Ber. 121 , 1329-1340 (1988), E. Bartmann, Adv. Mater. 8, 570-573 (1996) and M. Kuroboshi and T. Hiyama, Synlett. 1994, 251-252. Furthermore, the compounds can be prepared according or in analogy to the following reaction schemes.
  • R 3 , R 4 C-M O alkyl
  • the inventive chiral compounds can be used in a liquid crystal mixture for displays exhibiting a twisted molecular structure of the liquid crystal matrix like, for example, supertwisted or active matrix liquid crystal displays, or in displays comprising a liquid crystal mixture with a chiral liquid crystalline phase, like for example chiral smectic or chiral nematic (cholesteric) mixtures for ferroelectric displays or cholesteric displays.
  • a liquid crystalline mixture in particular a cholesteric liquid crystalline mixture, comprising at least one chiral compound of formula I.
  • cholesteric liquid crystal displays comprising a cholesteric liquid crystalline medium containing at least one chiral compound of formula I.
  • inventive compounds are especially characterized by a high solubility in liquid crystalline host mixtures. Therefore, they can be added as dopants to liquid crystalline hosts in high amounts without significant affecting the phase behaviour and electrooptical properties of the mixture. Furthermore, undesired spontaneous crystallization at low temperatures are reduced and the operating temperature range of the mixture can be broadened.
  • inventive chiral compounds with low values of the HTP can be used for the preparation of highly twisted liquid crystal media, because the dopant concentration can be increased to yield low pitch values (i.e. high twist) without affecting the mixture properties.
  • the use of a second dopant, which is often added to avoid crystallization, can thus be avoided.
  • liquid crystalline mixtures with a high helical twist i.e. a low pitch
  • inventive compounds with a moderate helical twist can be prepared already when using the inventive compounds as dopants in low amounts.
  • inventive compounds make them also suitable to be used in combination with other compounds for the temperature compensation of the properties of liquid crystal mixtures, such as the cholesteric pitch, and of the properties of displays, e.g. such as the threshold voltage.
  • inventive compounds are furthermore advantageous because they are affecting the physical properties of the liquid crystalline mixture only to a minor extent.
  • a liquid crystalline mixture according to the invention comprises preferably 0.1 to 30 %, in particular 1 to 25 % and very particularly preferably 2 to 15 % by weight of chiral compounds of formula I.
  • a liquid crystalline mixture according to the invention preferably comprises 1 to 3 chiral compounds of formula I.
  • the liquid crystalline mixture preferably contains a chiral component which contains at least one chiral compound of formula I, and a nematic component comprising one or more nematic or nematogenic compounds.
  • the liquid crystalline mixture consist of 2 to 25, preferably 3 to 15 compounds, at least one of which is a chiral compound of formula I.
  • the other compounds, forming the nematic component are preferably low molecular weight liquid crystalline compounds selected from nematic or nematogenic substances, for example from the known classes of the azoxybenzenes, benzylidene-anilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl esters of cyclohehexanecarboxylic acid, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl esters of benzoic acid, of cyclohexanecarboxylic
  • the liquid crystalline mixture of this preferred embodiment is based on the achiral compounds of this type.
  • U and E which may be identical or different, are in each case, independently from one another, a bivalent radical from the group formed by -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -Dio-, -B-Phe- and -B-Cyc- and their mirror images, where Phe is unsubstituted or fluorine-substituted 1 ,4-phenylene, Cyc is trans- 1 ,4-cyclohexylene or 1 ,4-cyclohexenylene, Pyr is pyrimidine-2,5-diyl or pyridine-2,5-diyl, Dio is 1 ,3-dioxane-2,5-diyl abd B is 2-(trans-1 ,4- cyclohexyl)ethyl, pyrimidine-2,5-diyl
  • R' and R" are, in each case, independently of one another, alkyl, alkenyl, alkoxy, alkenyloxy, alkanoyloxy, alkoxycarbonyl or alkoxycarbonyloxy with 1 to 18, preferably 3 to 12 C atoms, or alternatively one of R' and R" is F, CF 3 , OCF 3 , Cl, NCS or CN.
  • R' and R" are, in each case, independently of each another, alkyl, alkenyl or alkoxy with different chain length, wherein the sum of C atoms in nematic media generally is between 2 and 9, preferably between 2 and 7.
  • inventive compounds are in particular useful for anisotropic polymer gels and for low molar mass or polymerizable or polymerized cholesteric liquid crystalline mixtures for cholesteric displays, such as for example phase change displays or surface stabilized or polymer stabilized cholesteric texture displays (SSCT, PSCT).
  • SSCT surface stabilized or polymer stabilized cholesteric texture displays
  • chiral compounds of formula I in cholesteric liquid crystalline media for example for application in an SSCT or PSCT display, they exhibit good solubility in the nematic host mixture and induce a high helical twist with low temperature dependence of the helical pitch and the reflection wavelength.
  • cholesteric mixtures with high brightness of the reflection colour and low temperature dependence can be achieved even by using only one chiral dopant according to formula I, preferably in low amounts.
  • a particularly preferred embodiment of the present invention relates to a cholesteric liquid crystalline medium, in particular for use in SSCT and PSCT displays, comprising one chiral compound of formula I, preferably in an amount of 15 % or less, in particular 10 % or less, very preferably 5 % or less.
  • Another preferred embodiment relates to inventive chiral compounds with a strong temperature dependence of the HTP in nematic liquid crystal mixtures, which are useful for thermochromic media.
  • anisotropic polymer gels and displays comprising them are disclosed for example in DE 195 04 224 and GB 2 279 659.
  • SSCT and PSCT displays comprising the inventive compounds have reduced response times, lower voltages and improved contrast compared to displays comprising conventional dopants, like e.g. R 811 or CB 15, that are commercially available by Merck KGaA (Darmstadt, Germany).
  • conventional dopants like e.g. R 811 or CB 15, that are commercially available by Merck KGaA (Darmstadt, Germany).
  • SSCT and PSCT displays in which the conventional dopants are replaced by chiral compounds of according to the present invention can show reduced switching time.
  • Cholesteric films made by using the inventive compounds instead of prior art dopants show improved brightness, leading to a better contrast between the coloured planar texture and the almost clear focal conic state which is made black using a black backplate.
  • inventive chiral compounds and polymerizable liquid crystalline mixtures comprising these compounds are also particularly useful for the preparation of anisotropic polymer films with a chiral liquid crystalline phase, such as cholesteric or chiral smectic polymer films, in particular films that exhibit helically twisted molecular structure with uniform planar orientation, i.e. wherein the helical axis is oriented perpendicular to the plane of the film.
  • oriented cholesteric polymer films can be used as broad waveband reflective polarizers, as described e.g. in EP 0 606 940, as colour filters, for security markings, or for the preparation of liquid crystal pigments.
  • broad waveband reflective polarizers as described e.g. in EP 0 606 940
  • colour filters for security markings, or for the preparation of liquid crystal pigments.
  • I. Heynderickx and D.J. Broer in Mol.Cryst.Liq.Cryst. 203, 113-126 (1991 ) describe crosslinked cholesteric polymer films that are made of liquid crystalline diacrylates and contain a low molecular weight chiral dopant.
  • cholesteric polymer films made by using the inventive chiral compounds are brighter compared to films comprising dopants of prior art like e.g. R 811 or CB 15 as mentioned above.
  • the liquid crystalline mixture should comprise at least one polymerizable compound, preferably a polymerizable mesogenic compound, in additon to chiral compounds of formula I.
  • Another object of the invention are polymerizable liquid crystalline mixtures comprising at least one chiral compound of formula I and at least one polymerizable mesogenic compound.
  • the polymerizable CLC mixture comprises at least one polymerizable mesogenic compound having one polymerizable functional group and at least one polymerizable mesogenic compound having two or more polymerizable functional groups.
  • P has one of the meanings of formula I and its preferred meanings as mentioned above, x is an integer from 1 to 12 , A and D are 1 ,4-phenylene or 1 ,4-cyclohexylene, v is 0 or 1 , Y° is a polar group, R° is an unpolar alkyl or alkoxy group, Ter is a terpenoid radical like e.g. menthyl, Choi is a cholesteryl group, and L 1 and L 2 are each independently H, F, Cl, CN, OH, N0 2 or an optionally halogenated alkyl, alkoxy or carbonyl group with 1 to 7 C atoms.
  • the polar group Y° is preferably CN, N0 2 , halogen, OCH 3 , OCN, SCN, COR 5 , COOR 5 or a mono- oligo- or polyfluorinated alkyl or alkoxy group with 1 to 4 C atoms.
  • R 5 is optionally fluorinated alkyl with 1 to 4, preferably 1 to 3 C atoms.
  • the polar group Y° is are selected of F, Cl, CN, N0 2 , OCH 3 , COCH 3 , COC 2 H 5 ,
  • COOCH 3 COOC 2 H 5 , CF 3 , C 2 F 5 , OCF 3 , OCHF 2 , and OC 2 F 5 , in particular of F, Cl, CN, OCH 3 and OCF 3 .
  • the unpolar group R° is preferably an alkyl group with 1 or more, preferably 1 to 15 C atoms or an alkoxy group with 2 or more, preferably 2 to 15 C atoms.
  • a polymerizable CLC material according to the first preferred embodiment as described above comprises one or more chiral dopants which themselves do not necessarily have to show a liquid crystalline phase and give good planar alignment themselves, in particular non-polymerizable chiral dopants.
  • the mono- and difunctional polymerizable mesogenic compounds of above formulae V and VI can be prepared by methods which are known per se and which are described in the documents cited above and, for example, in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.
  • the polymerizable liquid crystalline mixtures comprise at least one inventive chiral compound, at least one monofunctional compound of formulae Va-Vm and at least one bifunctionaf polymerizable compound of formulae Vla-Vle.
  • the polymerizable liquid crystalline mixtures comprise at least one inventive chiral compound and at least two monofunctional compounds of formulae Va-Vm.
  • Another object of the invention is an anisotropic polymer film with an oriented chiral liquid crystalline phase obtainable by (co)polymerizing a liquid crystalline mixture comprising at least one chiral compound of formula I and at least one polymerizable mesogenic compound preferably selected of formula Va-Vm and Vla-Vle and/or at least one polymerizable chiral compound of formula I.
  • anisotropic polymer film with a chiral liquid crystalline phase with uniform orientation the inventive liquid crystalline mixtures, for example, are coated onto a substrate, aligned and polymerized in situ by exposing them to heat or actinic radiation. Alignment and curing are preferably carried out in the liquid crystalline phase of the liquid crystalline mixtures.
  • Actinic radiation means irradiation with light, like UV light, IR light or visible light, irradiation with X-rays or gamma rays or irradiation with high energy particles, such as ions or electrons.
  • a source for actinic radiation for example a single UV lamp or a set of UV lamps can be used.
  • Another possible source for actinic radiation is a laser, like e.g. a UV laser, an IR laser or a visible laser.
  • a photoinitiator when polymerizing by means of UV light, a photoinitiator can be used that decomposes under UV irradiation to produce free radicals or ions that start the polymerization reaction.
  • a photoinitiator for radical polymerization for example the commercially available Irgacure 651 , lrgacure 184, Darocure 1173 or Darocure 4205 (all from Ciba Geigy AG) can be used, whereas in case of cationic photopolymerization the commercially available UVl 6974 (Union Carbide) can be used.
  • the polymerizable liquid crystalline mixtures comprising polymerizable chiral compounds of formula I and/or polymerizable mesogenic compounds of formulae V and VI additionally comprise 0.01 to 10 %, in particular 0.05 to 8 %, very preferably 0.1 to 5 % by weight of a photoinitiator, especially preferably a UV-photoinitiator.
  • the polymerization of the polymerizable mesogenic material is carried out under an atmosphere of inert gas, preferably under a nitrogen atmosphere.
  • a substrate for example a glass or quarz sheet as well as a plastic film or sheet can be used. It is also possible to put a second substrate on top of the coated mixture prior to, during and/or after polymerization.
  • the substrates can be removed after polymerization or not.
  • at least one substrate has to be transmissive for the actinic radiation used for the polymerization.
  • Isotropic or birefringent substrates can be used.
  • the substrate is not removed from the polymerized film after polymerization, preferably isotropic substrates are used.
  • At least one substrate is a plastic substrate such as for example a film of polyester such as polyethyleneterephthalate (PET), of polyvinylalcohol (PVA), polycarbonate (PC) or triacetylcellulose (TAC), especially preferably a PET film or a TAG film.
  • PET polyethyleneterephthalate
  • PVA polyvinylalcohol
  • PC polycarbonate
  • TAC triacetylcellulose
  • PET films are commercially available from ICI Corp. under the trade name Melinex.
  • the inventive mixture of the polymerizable liquid crystalline mixture comprising a chiral compound of formula I is coated as a thin layer on a substrate or between substrate, and is preferably aligned in its chiral mesophase, eg. the cholesteric or chiral smectic phase, to give a planar orientation, i.e. an orientation so that the axis of the molecular helix extends transversely to the layer.
  • a planar orientation can be achieved for example by shearing the mixture, e.g. by means of a doctor blade. It is also possible to apply an alignment layer, for example a layer of rubbed polyimide or sputtered SiO x , on top of at least one of the substrates.
  • a second substrate is put on top of the coated material.
  • the shearing caused by putting together the two substrates is sufficient to give good alignment.
  • a second substrate not only to aid alignment of the polymerizable mixture but also to exclude oxygen that may inhibit the polymerization.
  • the curing can be carried out under an atmosphere of inert gas.
  • curing in air is also possible using suitable photoinitiators and high lamp power.
  • oxygen exclusion most often is not needed, but water should be excluded.
  • a polymerizable liquid crystalline mixture for the preparation of anisotropic polymer films comprises preferably 0.1 to 35 %, in particular 0.5 to 15 % and very particularly preferably 0.5 to 5 % by weight of one or more polymerizable chiral compounds of formula I.
  • Polymerizable liquid crystalline mixtures are preferred that comprise 1 to 3 chiral compounds of formula I.
  • inventive polymerizable liquid crystalline mixtures can additionally comprise one or more other suitable components, such as, for example, catalysts, sensitizers, stabilizers, co-reacting monomers or surface-active compounds.
  • the inventive polymerizable liquid crystalline mixture comprises a stabilizer that is used to prevent undesired spontaneous polymerization for example during storage of the composition.
  • stabilizers in principal all compounds can be used that are known to the skilled in the art for this purpose. These compounds are commercially available in a broad variety. Typical examples for stabilizers are 4-ethoxyphenol or butylated hydroxytoluene (BHT).
  • Typical examples for difunctional non mesogenic monomers are alkyldiacrylates or alkyldimethacrylates with alkyl groups of 1 to 20 C atoms.
  • Typical examples for non mesogenic monomers with more than two polymerizable groups are trimethylpropanetrimethacrylate or pentaerythritoltetraacrylate.
  • inventive compositions comprising compounds with only one polymerizable functional group leads to linear polymers, whereas in the presence of compounds with more than one polymerizable functional group crosslinked polymers are obtained.
  • liquid crystalline mixtures can be polymerized in situ as described above, however, in this case alignment of the polymerizable mixture is not necessary.
  • inventive chiral compounds of formula I can also be used for the prepration of thermochromic liquid crystalline mixtures.
  • inventive liquid crystalline mixtures with thermochromic behaviour that exhibit a cholesteric phase.
  • inventive liquid crystalline mixtures with thermochromic behaviour can be polymerizable or non- polymerizable.
  • the chiral compounds of formula and mixtures and polymers comprising them are also suitable for the preparation of liquid crystal pigments.
  • oriented cholesteric polymer films prepared as described above can be ground into small flaky particles, which are suitable as pigments showing selective reflection of light.
  • These pigments can be used for example in inks, paints or coatings for cosmetics, pharmaceutical, decorative or security applications.
  • the preparation of liuid crystal pigments is described for example in EP 601 483, WO 97/27252 or WO 97/30136.
  • Liquid crystal pigments comprising a chiral compound of formula I are another object of the present invention.
  • inventive chiral compounds of formula I and liquid crystalline mixtures, liquid crystal polymers or liquid crystal pigments comprising them are also suitable for use in cosmetic and pharmaceutical compositions, for example for coloured make-up as described in EP 815 826 or as UV-filters for the protection of human skin or hair, in particular protection against UV-A and UV-B-radiation, as described for example in DE 196 29 761 or EP 1 038 941.
  • inventive dopants have a high HTP, therefore only small amounts are needed to yield a short pitch, resulting in a material that shows reflection in the UV range and is suitable as UV-filter.
  • a liquid crystalline mixture, liquid crystal polymer or liquid crystal pigment comprising a chiral compound of formula I and reflecting UV light, in particular of a wavelength of 200 to 400 nm is another object of the invention.
  • Another object is a cosmetic composition, in particular a cosmetic or pharmaceutical composition for protection of human skin or hair, comprising as UV-filter a liquid crystalline mixture, liquid crystal polymer or liquid crystal pigment comprising a chiral compound of formula I and reflecting UV light, in particular in a wavelength range of 200-440 nm, especially 280-400 nm, 200-230 nm (UV-C) and 280-330 nm (UV-B).
  • HTP (p.c) "1 in ⁇ m "1 , wherein p is the pitch of the molecular helix, given in ⁇ m, and c is the concentration by weight of the chiral compound in the host given in relative values (thus, e.g. a concentration of 1 % by weight is corresponding to a value of c of 0.01 ).
  • K crystalline
  • N nematic
  • S smectic
  • N*, Ch chiral nematic, cholesteric
  • I isotropic.
  • HTP values of the examples were determined in the commercially available liquid crystal host mixture MLC-6260 (Merck KGaA, Darmstadt, Germany) at a concentration of 1 % and a temperature of 20 °C.
  • the separated aqueous phase was extracted with DCM. Celite was added to the combined organic phases and filtered off. The filtrate was washed with water and dried over Na 2 S0 4 . After evaporation of the solvent the residue was filtered in n-hexane with silica gel. The colourless crude product was purified by repeated recrystallization from n-pentane and filtration with silica gel in ether.
  • Compound (1) has the liquid crystal phase sequence K 37 S A 64 N* 87.7 I and a HTP of 7.53 at 20 °C with a low temperature dependence (7.65 at 0 °C and 7.36 at 50 °C).
  • Compound (2) has a melting point of 28 °C and a HTP of 6.22 at 20 °C.
  • Compound (3) has a HTP of -8.3 at 20 °C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Liquid Crystal Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

L'invention concerne des composés chiraux de formule (I) dans laquelle R?1, R2, A1, A2, X1, X2, Z3¿ et m ont les significations indiquées dans la revendication 1, des mélanges de cristaux liquides contenant au moins un composé chiral de formule (I), des polymères cristaux liquides linéaires ou réticulés obtenus par polymérisation d'un mélange polymérisable contenant au moins un composé chiral de formule (I), l'utilisation de composés chiraux de formule (I) et de mélanges et polymères, obtenus à partir de ces composés, dans des écrans à cristaux liquides, des éléments optiques actifs et passifs, des adhésifs, des résines synthétiques à propriétés mécaniques anisotropiques, des compositions cosmétiques et pharmaceutiques, des diagnostics, des pigments de cristaux liquides, pour applications décoratives et sécuritaires, des optiques non linéaires, des mémoires optiques ou en tant que dopants chiraux. Ladite invention concerne également un écran à cristaux liquides comprenant un mélange qui contient au moins un composé chiral de formule (I).
PCT/EP2001/007217 2000-07-13 2001-06-25 Composes chiraux i WO2002006196A1 (fr)

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AU2001266092A AU2001266092A1 (en) 2000-07-13 2001-06-25 Chiral compounds i
JP2002512103A JP5265838B2 (ja) 2000-07-13 2001-06-25 キラルな化合物ｉ
EP01943543A EP1299334B1 (fr) 2000-07-13 2001-06-25 Composes chiraux i
KR1020037000358A KR100849981B1 (ko) 2000-07-13 2001-06-25 키랄 화합물 ｉ
US10/332,470 US7060331B2 (en) 2000-07-13 2001-06-25 Chiral compounds 1
DE60132456T DE60132456T2 (de) 2000-07-13 2001-06-25 Chirale verbindungen i

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US20030175445A1 (en) 2003-09-18
KR100849981B1 (ko) 2008-08-01
EP1299334A1 (fr) 2003-04-09
JP5265838B2 (ja) 2013-08-14
EP1299334B1 (fr) 2008-01-16
TW538118B (en) 2003-06-21
AU2001266092A1 (en) 2002-01-30
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US7060331B2 (en) 2006-06-13
DE60132456D1 (de) 2008-03-06

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